Defence Science Journal, Vol. 58, No. 4, July 2008, pp.

504-516
Ó 2008, DESIDOC

Synthesis and Characterisation of Nanomaterials

P. Saravanan, R. Gopalan, and V. Chandrasekaran

Defence Metallurgical Research Laboratory, Hyderabad-500 058

ABSTRACT

Development of synthesis protocols for realising nanomaterials over a range of sizes, shapes,
and chemical compositions is an important aspect of nanotechnology. The remarkable size-
dependent physico-chemical properties of nanoparticles have fascinated and inspired research
activity in this direction. This paper describes some aspects on synthesis and characterisation
of nanoparticles of metals, metal alloys, and oxides, either in the form of thin films or bulk shapes.
A brief discussion on processing of two-phase nanocomposite magnets is also presented.

Keywords: Nanoparticle synthesis, self-assembly, thermal decomposition, liquid-liquid interface

reaction, ball milling

1. INTRODUCTION them. Self-assembly of nanoparticles synthesised by

There is a tremendous research interest in the
area of nanotechnology to develop reliable processes
for the synthesis of nanomaterials over a range of
sizes and chemical compositions. Although the conventional
methods of synthesis of metal sols, known since the
times of Michael Faraday, continue to be used for
generating metal nanoparticles, there have been several
improvements and modifications in the methods which
provide a better control over the size, shape, and
other characteristics of the nanoparticles1,2. These
developments have enabled studies of quantum confinement
as well as other properties dependent on size, shape,
and composition3. Ligating nanoparticles with organic
molecules and assembling these in one-, two-, or
three-dimensional mesostructures have added another
dimension to this field wherein collective properties
of nanoparticles have been of special interest4. The
exciting potential of nanomaterials can be en routed
to nanodevice applications, only with a combination
of nanobuilding units and strategies for assembling
Received 04 June 2007, revised 13 September 2007
504
the colloidal route on suitable supports is one of the
interesting techniques currently being investigated
for realising such structures5. Though the synthesis
and organisation of nanoparticles provide complementary
tools for nanotechnology, processing of nanoparticles
or nanopowders into bulk shapes, retaining nanosize
is another challenging aspect, as far as structural and
engineering applications are concerned.
Synthesis and assembly strategies of nanoparticles
mostly accommodate precursors from liquid, solid
or gas phase; employ chemical or physical deposition
approaches; and similarly rely on either chemical
reactivity or physical compaction to integrate the
nanostructure building blocks within the final material
structure. The variety of techniques that can be
classified in top-down or bottom-up approaches
are schematically illustrated in Fig. 1. The bottom-
up approach of nanomaterials synthesis first forms
the nanostructured building blocks (nanoparticles)
and then assembles these into the final material.
 SARAVANAN, et al.: SYNTHESIS AND CHARACTERISATION OF NANOMATERIALS
An example of this approach is the formation
of powder components through aerosol and sol-gel
techniques and then the compaction of the components
into the final material. Nanoparticles with diameters
ranging from 1 nm to 10 nm with consistent crystal
structure, surface derivatisation, and a high degree
of monodispersity can be processed by these techniques6.
Gas phase synthesis or aerosol processing of
nanoparticles is based on evaporation and condensation
(nucleation and growth) in a subatmospheric inert-
gas environment; and the processing mainly is by
combustion flame, laser ablation, chemical vapour
condensation, spray pyrolysis, electro spray, and
plasma spray.
On the other hand, sol-gel processing is a wet
chemical synthesis approach that can be used to
generate nanoparticles by gelation, precipitation,
and hydrothermal treatment. Besides, better size
and stability control of nanoparticles can be achieved
using inverted micelles, polymer-matrix architecture
based on block copolymers or polymer blends, and
ex situ particle-capping techniques. Additional
nanoparticle synthesis techniques include sonochemical
processing, hydrodynamic cavitation, and microemulsion
processing. In sonochemistry, an acoustic cavitation
process can generate a transient localised hot zone
with extremely high temperature gradient and pressure8.
Such sudden changes in temperature and pressure
assist the destruction of the sonochemical precursor
(e.g., organometallic solution) and the formation of
nanoparticles. The technique can be used to produce
a large volume of material for industrial applications.
NANOSTRUCTURED MATERIAL
"BOTTOM-UP"
ASSEMBLE FROM
NANO-BUILDING BLOCKS
· POWDER/AEROSOL COMPACTION
· CHEMICAL SYNTHESIS
Figure 1. Schematic of a variety of nanostructure synthesis and assembly approaches.
In hydrodynamic cavitation, nanoparticles are generated
through creation and release of gas bubbles inside
the sol-gel solution 9. By rapidly pressurising in a
supercritical drying chamber and exposing to cavitational
disturbance and high temperature heating, the sol-
gel solution is mixed. The erupted hydrodynamic
bubbles are responsible for nucleation, growth, and
quenching of the nanoparticles. Particle size can
be controlled by adjusting the pressure and the
solution retention time in the cavitation chamber.
Microemulsions are another important processing
technique-extensively used for synthesis of metallic,
semiconductor and magnetic nanoparticles 10,11. By
controlling the very low interfacial tension (~10–3 mN/m)
by adding a cosurfactant (e.g., an alcohol of intermediate
chain length), these microemulsions are produced
spontaneously without the need for significant mechanical
agitation. The technique is useful for large-scale
production of nanoparticles using relatively simple
and inexpensive hardware.
The top-down approach begins with a suitable
starting material and then sculpts the functionality
from the material. This technique is similar to
the approach used by the semiconductor industry
in forming devices out of an electronic substrate
(silicon), utilising pattern formation (such as electron
beam lithography) and pattern-transfer processes
(such as reactive-ion etching) that have the requisite
spatial resolution to achieve creation of structures
at the nanoscale. This particular area of nanostructure
formation has tremendous scope and is a driving
issue for the electronics industry. Another top-
"TOP-DOWN"
‘SCULPT’ FROM BULK
· MECHANICAL ATTRITION
(BALL MILLING)
· LITHOGRAPHY/ETCHING
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 DEF SCI J, VOL. 58, NO. 4, JULY 2008
down approach is ball milling, the formation of
nanostructure building blocks through controlled
mechanical attrition of the bulk starting material 12.
Those nano building blocks are then subsequently
assembled into a new bulk material. The technique,
already a commercial technology, has been considered
dirty because of contamination problems from
ball-milling processes. However, the availability
of tungsten carbide components and the use of
inert atmosphere and/or high vacuum processes
have reduced impurities to acceptable levels for
many industrial applications.
In fact, many current strategies for nanomaterial
synthesis integrate both synthesis and assembly
into a single process with efforts to have a better
control over size, shape, and structure. Over the
last several years, numerous physical and chemical
methods have been employed to produce nanoparticles.
The R&D status of these methods has gone up by
an order of magnitude in the past five years due
to the demand of the nanotechnology. A sampling
of the leading institutions in India involved in various
areas of nanomaterials research include, almost all
the universities, IITs, IISc, JNCASR, DRDO, CSIR,
DST, and other national laboratories. Each of these
laboratories/institutions is involved in the core areas
of research such as synthesis, assembly, and
characterisation of nanoparticles, nanotubes, nanowires,
nanoporous solids, nanostructured alloys, and DNA
chips, etc. Some of the products being developed
with the nanomaterials include NEMS-based thermal
sensors, value-added fabrics, nanoparticle-based
drug delivery systems, magnetic nanoparticles for
therapeutic use, super-hard coatings, flexible display,
biosensors, and nanopatterned surfaces.
The DMRL, being a metallurgical laboratory,
is actively engaged in various activities of nanomaterials,
which include, development of nanocomposite magnets
through high-energy ball milling, piezoelectric ceramics
by sol-gel method, metal-metal alloy particles by
soft chemical method, and also characterisation of
various nanomaterials by TEM and 3-D atom probe.
In this paper, some of the important methods, highly
suitable for either preparing films of nanoparticles
or processing these into bulk shapes, are briefly
presented.
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2. SYNTHESIS OF NANOMATERIALS
The organisation of nanoparticles in a thin film
form is often necessary to render these functional
and operational. Two important chemical methods:
(a) high-temperature thermal decomposition and
(b) liquid-liquid interface reaction, suitable for preparing
films of many metal and metal oxide nanoparticles,
are illustrated with examples. In addition, the
utilisation of a high-energy ball milling and spark
plasma sintering process for the preparation and
processing of nanocomposite powders into bulk
magnets are also highlighted.
2.1 High-temperature Thermal Decomposition
A general scheme for preparing mono-disperse
nanoparticles requires a single, temporally short
nucleation event followed by slower growth on the
existing nuclei. This may be achieved by quick
addition of reagents into a reaction vessel containing
a hot coordinating solvent. The temperature of the
solution is sufficient to decompose the reagents,
forming a supersaturation of species in solution
that is relieved by nucleation of nanoparticles. High-
temperature thermal decomposition provides a general
route for preparing dispersable nanoparticles of
most of the transition-metal oxides using metal
cupferron complexes MxCup X (M: metal ion; Cup:
N-nitroso-N-phenylhydroxylamine, [C6H 5N(NO)O –]
are used as single-molecular precursors 13 . In this
non-hydrolytic route, the cupferron complex (which
binds the metal ion through oxygen) is decomposed
by releasing a leaving group such as nitrosobenzene
at 250–300 °C in a hot coordinating solvent [Fig. 2(a)].
The resulting product forms a stable suspension
consisting of oxide nanoparticles; each nanoparticle
in a sample consists of an inorganic crystalline
core surrounded by an organic monolayer (surfactant).
The nanoparticles so obtained are freely soluble
in non-polar organic solvents and can be readily
precipitated from solutions with polar solvents. Further,
nanoparticles with uniform size distribution (s < 7 %)
can be achieved through size-selective precipitation
procedures and the organic monolayer coordinating
each nanoparticle surface enables to self-assemble
into nanoparticle superlattices under controlled
conditions. Thus, ordered nanoparticles assemblies/
 SARAVANAN, et al.: SYNTHESIS AND CHARACTERISATION OF NANOMATERIALS
monolayer thin films are obtained using this method.
The experimental procedure is schematically
represented in Fig. 2(b).
The characteristic advantages of this colloidal
route are: (i) besides producing dispersable nanoparticles
of almost all transition-metal oxides, this method
enables to prepare ordered nanoparticle assemblies
N-OCTYLAMINE/
´ TRIOCTYLAMINE
M CUP´ (MO)´ + C6H5NO
Ar/250 °C
´ ´
M : metal ion in the oxidation state ´ (M =Fe3+, Co2+, Zn2+, etc.);
CUP: N-NITROSO-N-PHENYLHYDROXYLAMINE, C6H5N(NO)O-
(a)
(i)
(ii)
(iii)
(iv)
(b)
Figure 2. (a) Reaction scheme for the preparation of metal
oxide nanoparticles, and (b) schematic
representation of steps involved in obtaining ordered
nanoparticle assemblies: (i) synthesis of
nanoparticles by thermal decomposition, (ii)
narrowing the nanoparticle sample by size-selective
precipitation, (iii) deposition of nanoparticle
dispersions to self-assemble, and (iv) ordered
nanoparticle assemblies (superlattices).
with appropriate choice of surfactants, (ii) using
suitable ratio of bi-metal precursors, spinel ferrite
nanoparticles can also be obtained, (iii) the reaction
atmosphere employed in this method also plays
critical role in determining the nature of the
nanoparticles; and (iv) with the same precursor,
one can prepare either oxide or sulphide nanoparticles
by maintaining Ar or H 2S atmosphere during thermal
decomposition. Following are some of the above
facts demonstrated with specific examples:
At first, the precursor materials, i.e., metal
cupferron complexes were prepared by aqueous
precipitation, by cooling a solution of 5 g of respective
metal chlorides in 100 ml of water to 0 °C and then
adding 5 per cent by weight filtered aqueous cupferron
solution, at suitable pH 14 . The obtained precipitates
were washed several times with water and dried.
The precursor materials were then recrystallised
from methanol and characterised by thermogravimetry.
Synthesis of several magnetic oxide nanoparticles
including g-Fe2O3, Fe3O4, and Co3O4 and semiconductor
nanoparticles such as, ZnO and ZnS have been
performed by decomposing respective metal cupferron
complexes in the presence of a hot coordinating
solvent.
In a typical synthesis yielding g-Fe2O3 nanoparticles,
a 0.3 mM solution of iron cupferron complex in
n-octylamine was injected into a vigorously stirred
9 ml solution of tri-n-octylamine at ~300 °C in a
round bottomed flask. The onset of reduction was
marked by change in colour from red-brown to
brown-black with brisk effervescence. The contents
of the flask were maintained at ~225 °C and the
stirring continued for another 45 min. To obtain
Fe 3O 4 particles, the decomposition of cupferronates
was carried out in H 2 atmosphere and the contents
of the flask were maintained at ~250 °C till a
colour change from brown to black was observed 15 .
In a similar manner, Mn 3O 4, Co 3O 4 , Cu 2O, and
ZnO nanoparticles can be prepared by the thermal
decomposition of respective cupferron complexes
in Ar atmosphere 13.
Representative TEM images of typical magnetic
oxides of g-Fe 2O 3, Fe3 O 4, and Co 3O 4 (Fig. 3) show
the successful synthesis of various uniform magnetic
nanoparticles through this thermal decomposition
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 DEF SCI J, VOL. 58, NO. 4, JULY 2008
method. The 2-D assembly of n-octylamine capped
Co3 O 4 [Fig. 3(b)] and dodecylamine capped Fe 3 O 4
[Fig. 3(d)] occurred spontaneously on the copper
TEM grids after the evaporation of the solvents,
indicating the regular shapes and narrow size distribution
of these nanoparticles.
In Fig. 4, typical TEM micrographs of n-octylamine
capped ZnO and ZnS nanoparticles obtained by
thermal decomposition of zinc cupferron complex
under Ar and H 2 S atmosphere respectively, are
shown16. Besides synthesising oxide and sulphide
nanoparticles, by adopting bi-metal precursors in
a certain mole ratio, composite oxide nanoparticles
such as magnetic MFe 2O 4 (M represents Fe, Co,
Mg, Zn or Mn) could be effectively prepared following
this synthetic approach. Figure 5 depicts the typical
micrographs of CoFe2O 4 and MnFe 2O 4 spinel ferrite
nanoparticles with dia ~10 nm, which formed 2-
D patterns on the TEM grids and showed good
(a) g-Fe2O3
20 nm
(c) Fe3O4
20 nm
Figure 3. TEM micrographs of n-octylamine capped: (a) g-Fe2O3 , (b) Co 3O4 , (c) Fe 3O4 , and (d) dodecylamine capped Fe3O4
nanoparticles, (Insets: SAED patterns).
508
uniformity 17 . The details of structural and magnetic
properties of the nanoparticles prepared by this
technique are described by Saravanan 15-16 , et al.
With the above examples, it is thus demonstrated
that the thermal decomposition is one of the most
general approaches for the preparation of transition
metal oxide/sulphide colloidal nanoparticles.
2.2 Liquid-liquid Interface Reaction
Nanoparticles anchored to surfaces in the form
of film are considered to be important because of
their potential use in nanodevices. A liquid-liquid
interface offers potential to synthesise nanoparticles,
as well as casting them into a film. At a liquid-
liquid interface, the particles are highly mobile and
rapidly achieve an equilibrium assembly18. In contrast
to the other techniques, this method is a one-step
process enabling synthesis of nanparticle arrays at
the liquid-liquid interface under ambient conditions.
(b) Co3O4
(d) Fe3O4
 SARAVANAN, et al.: SYNTHESIS AND CHARACTERISATION OF NANOMATERIALS

Figure 4. TEM micrographs of n-octylamine capped: (a) ZnO and (b) ZnS semiconductor nanoparticles, (Insets: SAED patterns).

(a) C o Fe 2 O 4 (b ) M n F e 2O 4

20 n m 50 n m

Figure 5. TEM micrographs of n-octylamine capped magnetic spinel ferrite nanoparticles: (a) CoFe2O4 and (b) MnFe 2O4.

This method involves the reaction of an organo-
metallic compound dissolved in the organic layer
with a reducing, a sulphiding, or an oxidising agent
in the aqueous layer. The material formed at the
interface corresponds to an ultrathin nanocrystalline
film consisting of closely- packed nanocrystals coated
with the organic species present at the interface.
The novelty of this method is that it involves
a finite growth rate of the ultrathin nanocrystalline
film with controllable parameters such as temperature
and concentration. The nanocrystals in the films
can be readily extracted to aqueous or organic
layers by adding suitable capping agents. Further,
the nanocrystalline film obtained at the interface
can be easily transferred onto a solid support such
as mica or a polymer film. With appropriate choice
of metal precursors and reducing agents, a variety
of nanocrystalline films can be fabricated, and some
of the typical results obtained by this method are
presented to illustrate its versatility.
Nanocrystalline films of Au, Ag, and Cu have
been prepared at the toluene-water interface by the
interaction of their metal-triphenyl complexes in the
organic layer with partially hydrolyzed tetra-kis-hydroxy-
methyl-phosphonium chloride (THPC) in the aqueous
layer19. In a typical preparation, 10 ml of 1.5 mM
solution of Au(PPh 3)Cl in toluene was allowed to
stand in contact with 16 ml of 6.25 mM aqueous
alkali in a 100 ml beaker under ambient conditions.
Once the two layers got stabilised, 330 µl of 50 mM
THPC was injected into the aqueous layer using a
syringe with minimal disturbance to the toluene layer.
The onset of reduction was marked by a faint pink
coloration of the liquid-liquid interface. The reduction
thus initiated was allowed to proceed without disturbance
for several hours. With the passage of time, the
colour became more vivid, finally resulting in a robust
elastic film at the interface.
An important feature of the liquid-liquid interface
method is that the nanocrystals at the interface

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can be transferred to either aqueous or organic
phase using appropriate capping agents. For example,
by adding of dodecanethiol to the organic layer,
the Au nanocrystals could be transferred entirely
to the organic layer, while the addition of
mercaptoundecanoic acid transferred the nanocrystals
to the aqueous layer.
The transfer of Au nanocrystals to the aqueous
or the organic medium is marked by the acquisition
of a vivid colour by the respective layer, as demonstrated
in Fig. 6(a). The UV-visible spectra of the as-
prepared Au film as well as of the hydrosol and
organosol are shown in Fig. 6(b). All the spectra
exhibit bands due to the surface plasmon, the position
and intensity depending on several factors such as
the diameter of the nanocrystals, the nature of the
ligand, and the refractive index of the surrounding
medium. The film on quartz substrate exhibits a
broad band centred at 575 nm, while the sols show
plasmon bands at ~530 nm.
Films of other metals such as Ag and Cu could
be obtained by a similar procedure using Ag2(PPh3)4Cl2
and Cu(PPh 3)Cl, as metal precursors and the typical
TEM images of nanocrystalline films of Au, Ag,
and Cu are shown in Fig. 7. It can be seen that
all the micrographs consist of close-packed nanocrystals
with narrow size distribution, indicating that the
effectiveness of this technique on required control
of particle size distribution. Further, the size of the
metal nanocrystals formed at the liquid-liquid interface
can be controlled by adjusting the various reaction
parameters such as contact time, temperature, and
concentration of the reactants. By this means, the
optical and electrical properties of the films can
be varied 20.
Besides synthesising the films of Au, Ag, and
Cu nanoparticles, films of CuO nanowhiskers with
diameters in the range 50 nm to 300 nm and lengths
of up to several microns could be prepared by
employing reactions at the liquid-liquid interface21 .

(left) (middle) (right)

(a) (b)
Figure 6. (a) Nanocrystalline film of Au formed at the toluene-water interface (middle). When dodecanethiol was added to the
toluene layer, the film broke forming an organosol (left); while mercaptoundecanoic acid added to water produced
a hydrosol (right), and (b) UV-visible spectra of the as-prepared standard film on a synthetic quartz substrate (dark
line), octylamine capped nanocrystals in toluene (dashed line), and mercaptoundecanoic acid-capped nanocrystals in
water (dotted line).

(a) Au (b) Ag (c) Cu

50nm 50nm 50nm

Figure 7. TEM micrographs of the as-prepared nanocrystalline films: (a) Au, (b) Ag, and (c) Cu.

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 SARAVANAN, et al.: SYNTHESIS AND CHARACTERISATION OF NANOMATERIALS

In a typical preparation, 0.04 m mol of copper
acetyl-acetonate in 10 ml of toluene was allowed
to stand in contact with equal amount of aqueous
layer containing 1 m mol of NaOH. Once the two
layers were stabilised; the aqueous-organic interface
was kept in a waterbath at 50 °C for 60 min,
without disturbance. Reaction was complete, as
could be evidenced by a colour change of the
organic phase from blue to colourless, following
which the appearance of a black-brown coloured
CuO film at the liquid-liquid interface could be
discerned. Figure 8(a) depicts typical TEM image
of an as-prepared standard CuO film which reveals
that the film consists of a rod-like structure, extending
up to several hundred nm in length. Figure 8(b)
shows a corresponding SEM micrograph of the
CuO film, indicating dense-packing of needle- shaped
nanowhiskers, with exceptionally large aspect ratios.
The growth of these whiskers was scattered along
the interface layer and the overall film morphology
resembled a bamboo shoot-like structure.
Figure 8(c) shows the XRD pattern of the as-
prepared nanocrystalline CuO film. All the diffraction
peaks could be indexed to monoclinic CuO with
lattice constants: a = 0.4689 nm, b = 0.34288 nm
and c = 0.5142 nm, which are in good agreement
with the bulk CuO. To further verify the phase of
nanowhiskers, i.e., CuO or Cu 2O type, the as-
prepared film was annealed to 300 °C in the air
for about 6 h. The XRD analysis of annealed sample
apparently showed no evidence of oxidation of the
sample; indicating that the as-prepared film was
purely that of CuO. It was demonstrated that the
nature of the emerging film at the interface was
dependent on the factors such as temperature of

(a) (b)
(111)
(111)
_

Ann ealed at 300 °C

(202)

(020)
_

(202)
(113)
_

As-pre pared

20 40 60
2 (degre es)
(c)

Figure 8. (a) TEM micrograph of as-prepared CuO nanowhiskers obtained from a toluene water interface at 50 °C, (Inset: SAED
pattern), (b) SEM micrograph of as-prepared CuO film, and (c) XRD patterns of CuO film obtained at the interface.

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 DEF SCI J, VOL. 58, NO. 4, JULY 2008
the medium, contact time at the interface, relative
amounts of reducing agent, and metal precursor.
It is noteworthy that this simple approach requires
neither sophisticated techniques nor metal catalysts
and surfactants for the large-scale synthesis of
monoclinic CuO nanowhiskers.
In addition to the above examples, the applicability
of this technique in preparing a variety of nanocrystalline
films of metals, oxides, chalcogenides22, bi-metal
and tri-metal alloys23 has been recently demonstrated.
So, undoubtedly the liquid-liquid interface can be
considered as a promising method for the synthesis
of films of nanocrystals.
2.3 High-energy Ball Milling
Despite the fact that the chemical methods
have been widely employed for nanomaterial preparation;
the utilisation of physical methods has also been
given considerable attention; particularly in the
area of nanoengineered materials, wherein large-
scale fabrication of nanopowders is essential for
processing these into bulk shapes 24. Among the
physical methods, mechanical milling has been widely
utilised for the preparation of nanohard/nanocomposite
magnetic powders owing to its versatility. Mechanical
milling is a high-energy deformation process that
progressively introduces defect structures (dislocations
and vacancies), atomic-scale chemical disorder,
and elastic strain energy into the initially crystalline
starting powders through the shearing actions of
ball-powder collisions. Milling can be used to produce
a variety of effects in intermetallic alloys due to
complex dependence of the nanostructure on milling
intensity, temperature and other factors. The preparation
of nanocomposite magnetic powders of SmCo 5/Fe
through high-energy ball milling method and their
consolidation into bulk magnets using a spark plasma
sintering method has been demonstrated.
Nanocomposite permanent magnetic materials
consisting of hard (SmCo5 ) and soft (Fe or Fe-Co)
magnetic phases have immense potential to exhibit
a higher energy product than the conventional single-
phase hard magnets. It is predicted that the energy
product, [(BH) max] in a nanocomposite magnet can
be enhanced from that of a single-phase hard magnet,
using high saturation magnetisation of the soft phase
512
and the high coercivity of the hard phase if the two
phases are spring exchange coupled 25. Since the
magnetic properties and the degree of exchange
coupling are strongly dependent on the microstructural
parameters, such as crystallite size, phase distribution,
and volume fraction of the hard and soft magnetic
phases, many efforts have been made to synthesise
and characterise the nanostructured magnets by
mechanical milling, melt spinning, and thin-film
techniques. However, the consolidation of nanocomposite
powders into bulk-shaped magnets is a challenging
one and the bulk-shaped magnets are very essential
for any critical engineering application. Among all
the techniques used for consolidation (hot isostatic
pressing and plasma pressure compaction), the recently
developed spark plasma sintering (SPS) technique
has been successfully adopted to produce bulk
nanocomposite magnets with high coercivity and
excellent magnetic properties. In the SPS technique,
simultaneous application of pressure and rapid heating
rate (400–500 °C/min) by a pulsed electrical current
with dc bias voltage helps in densification without
causing grain growth.
The authors’ recent investigation on the preparation
of SmCo5 /x Wt per cent Fe nanocomposite powders
by high-energy ball milling and their consolidation
into bulk shape by SPS technique26 has been presented.
Figure 9 represents the various steps involved in
the preparation of nanocomposite magnets. SmCo 5
alloys were prepared by induction melting of the
elemental Sm and Co in Ar atmosphere. The as-
cast alloy ingot was crushed into coarse powders
with a typical particle size of ~300 mm. The alloy
powders were then mixed with a-Fe powders of
particle size < 10 mm and milled in a planetary ball
mill with a ball-to-powder ratio of 10 : 1 for different
milling time (4–50 h) at a constant speed (200 rpm).
The ball milling was carried out using tungsten carbide
balls and vial in toluene medium. The milling was
stopped at regular intervals to collect the powders
for intermediate structural and magnetic analyses.
The milled powder (10 h) was packed in a graphite
die of 15 mm inner dia for consolidation purpose
and a magnetic field of 2T was applied to orient the
powders prior to SPS. The aligned powders were
then subjected to SPS in vacuum (10 –3 Torr). The
SPS conditions were as follows: (i) sintering temperature
 SARAVANAN, et al.: SYNTHESIS AND CHARACTERISATION OF NANOMATERIALS
SmCo55 alloy
alloy
preparation
Preparation
SynthesisofofSmCo
Synthesis SmCo /Fe
5 5/Fe
nanocomposite powders
nanocomposite powders
Consolidation
Consolidation of
of nanopowders
nanopowders
into bulk
into bulkmagnets
magnets
Characterization
Characterisation
Figure 9. Flow chart showing various steps involved in the processing of nanocomposite magnets.
700–740 °C, (ii) pressure 10.0–10.5 kN, and (iii)
sintering time 5 min.
A bulk magnet with density of about 8.1 g/cc
(~96 %) was obtained after SPS compaction [Fig.
10(a)]. A typical TEM microstructure of SPS samples
shown in Fig. 10(b), clearly reveals that the sample
consists of randomly oriented nanograins, with an
average grain size of 20 nm. The inset in Fig. 10(b)
shows the nanobeam diffraction pattern taken along
[2 1 3 0 ] zone axis of one of the SmCo5 grains.
Demagnetization curves of the spark plasma sintered
nanocomposite SmCo 5 + x Wt per cent Fe (x = 5
and 10) samples are shown in Fig. 11. The smooth
demagnetisation curves and enhanced magnetisation
of SmCo 5+Fe samples indicate the existence of
strong exchange coupling between the hard and
soft magnetic phases.
(a)
Figure 10.(a) Bulk SmCo5 magnet after SPS compaction, and (b) corresponding TEM micrograph, (Inset: Nanobeam diffraction
pattern of the SmCo 5 phase).
Induction
Induction
melting
melting
Ball -milling
Ball-milling
Spark plasma
Spark plasma
sintering
sintering
SEM,TEM, XRD
and VSM
VSM
From Fig. 9, it can be seen that the SmCo5
phase without addition of Fe has coercivity (H c )
of 12 kOe and saturation magnetisation (M s) of
72 emu/g at a maximum applied field of 7T. The
SmCo 5+5 Wt per cent Fe sample has H c of 8.9 kOe
and M s of 86 emu/g, while SmCo 5+10 Wt per cent
Fe sample showed a coercivity of 7 kOe and saturation
magnetisation of 96 emu/g. It is clear from the
magnetic characterisation that with the increase of
Fe volume fraction, the magnetisation increases,
revealing the existence of a strong exchange coupling
between the nanosized hard (SmCo5 ) and soft (Fe)
magnetic phases. The energy products obtained in
the SPS samples are in the range 8–10 MGOe. The
relatively lower energy products obtained in the
samples are attributed to the randomness of the
nanograins as evidenced from TEM studies. To
(b)
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 DEF SCI J, VOL. 58, NO. 4, JULY 2008
a: SmCo5
b: SmCo5 + 5 wt % Fe
c: SmCo5 + 10 wt % Fe
–12000 –10000 –8000
MAGNETIC FIELD (Oe)
Figure 11. Demagnetisation curves of spark plasma sintered magnets.
conquer this problem, substantial efforts are being
made to achieve anisotropic hard magnetic particles
with nanosized grains by employing surfactant-
assisted or magnetic field-assisted ball milling
processes 27 .
3 . CONCLUSIONS
In this study, some salient aspects of chemical
synthesis strategies such as high-temperature thermal
decomposition and liquid-liquid interface reaction,
and physical method such as high-energy ball milling
suitable for either preparing films of nanoparticles
or processing these into bulk shapes, have been
presented. The potential of these techniques to
prepare a variety of metal/metal oxide nanoparticles,
films and two-phase nanocomposites has also been
highlighted with suitable examples.
ACKNOWLEDGEMENTS
The keen interest shown by the Director, DMRL
in this study is gratefully acknowledged. Besides,
Dr P. Saravanan sincerely acknowledges Director,
DMSRDE, Kanpur, and Prof C.N.R. Rao at JNCASR,
Bangalore, where the part of the study was carried
out. Authors also thank Shri N.V. Rama Rao for
his contributions on processing of nanocomposite
magnets.
514
60
50
MAGNETISATION (emu/g)
40
30
20
10
0
–6000 –4000 –2000 0
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Contributors

Dr P. Saravanan obtained his PhD from Bharathiar University, Coimbatore. Presently

he is working at the Defence Metallurgical Research Laboratory (DMRL), Hyderabad.
His areas of research include: Nanomaterials by chemical synthesis, nanocomposite
magnets, and thin films. He has more than 20 papers in international journals.
He is recipient of ISCA Young Scientist Award in Material Sciences (2000) by
Indian Science Congress Association, Kolkata; DRDO Young Scientist Award
(2003); and DRDO National Science Day Medal (2005).

Dr R. Gopalan is working in the Advanced Magnetic Group, DMRL, Hyderabad.

He obtained his PhD from the Indian Institute of Technology (IIT) Madras, Chennai.
He is heading nanostructured magnetic activity at DMRL and his area of specialisation
is: Magnetic materials and their structure-property correlation. He has published
more than 60 papers in international journals and has two patents to his credit.
He is the recipient of Laskar Memorial Prize for the Best PhD Thesis in Physics,
at IIT Madras, Chennai. He has also obtained National Science Day Medal (2006).

Dr V. Chandrasekaran is working as Head, Advanced Magnetic Group, DMRL,

Hyderabad. He obtained his PhD from Annamali University, Tamil Nadu. His areas
of research interest include Rare earth permanent magnets, magnetostrictive,
magnetocaloric, ferromagnetic shape memory, and nanostructured soft/hard materials.
He has published more than 40 papers in international journals. He is a recipient
of MRSI Medal (1990), Vasvik Industrial Research Award (1991), and Metallurgist
of the Year Award (1998).

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